The development of new catalytic methodologies for the precision synthesis of carbon-carbon bonds is central to the advancement of synthetic organic chemistry. Significant focuses of these efforts are made on the enantio- and diastereoselective synthesis of carbon frameworks, especially as chemists and biologists become more aware of the impact of nature’s inherent chirality on the efficacy of developed pharmaceutical agents. A powerful technique for enhancing the reactivity and selectivity of catalytic processes is through the use of multiple catalysts or activation modes, collectively deemed “cooperative catalysis.” This Dissertation describes several advances in the field of cooperative catalysis from our experimental and theoretical efforts. The first Chapter details our development, implementation, and mechanistic and computational study of a unique cooperative catalytic system utilizing chiral phosphoric acids and hydrogen bond donors for the synthesis of tetrahydropyranoindoles. The second Chapter delves into cooperative small-molecule and chemoenzymatic catalysis with our development of an N-heterocyclic carbene/ketoreductase dynamic kinetic resolution system for the production of enantio- and diastereoenriched γ-lactones. Finally, the third Chapter details our preliminary experimental and computational investigations into the organocatalytic capacity of a class of redox-active N-heterocyclic carbenes derived from naphthoquinone.

Creator

• Maskeri, Mark Andrew

DOI

• https://doi.org/10.21985/n2-ja02-4z98

Subject

• Organic chemistry
• Chemistry

Language

• en

Alternate Identifier

• etdadmin_upload_749341
• http://dissertations.umi.com/northwestern:15159

Keyword

• cooperative
• tetrahydropyranoindole
• catalysis
• chemoenzymatic
• chiral phosphoric acid
• lactone

Date created

• 2020-01-01

Resource type

• Dissertation

Rights statement

• In Copyright